A novel strategy has been developed for preparing porous carbon materials derived from taro stems, aimed at enhancing electromagnetic wave (EMW) attenuation and thermal energy storage. The materials were synthesized through the carbonization of taro stems to form a porous carbon structure, subsequently enhanced with polyethylene glycol (PEG) containing carbon nanotubes (CNTs) and nickel (Ni) nanoparticles. By adjusting the carbonization temperature and the loading of CNTs and Ni, the resulting carbon materials exhibited exceptional EMW attenuation performance. Specifically, the PC-800 sample demonstrated a remarkable minimum reflection loss of −61.4 dB across the frequency range of 8.2–11 GHz, with a low density of 0.054 g/cm³. The PC-1200 sample exhibited EMI SE values of 23.6 dB axially and 21.5 dB radially in the X-band, with an ultra-low density of 0.033 g/cm³. Further enhancements were observed in the PC/CNT2 and PC/CNT2-Ni15 composites, achieving EMI SE values of 26.3 dB and 26.8 dB, respectively. Additionally, these composites exhibited effective thermal energy storage and release, as confirmed by heating experiments. This study not only introduces a method for creating absorption-dominated biomass electromagnetic shielding materials but also provides a dual-functional solution for enhancing the performance of electronic devices.